CN104718249A - Film with low OCS gel index - Google Patents

Abstract

Process for providing a polypropylene composition comprising a branched polypropylene in which a polypropylene with a melt flow rate MFR2 (230 DEG C) of more than 1.0g/10min is reacted with a thermally decomposing free radical-forming agent and optionally with a bifunctionally unsaturated monomer obtaining thereby the branched polypropylene,wherein the polypropylene composition has a F30 melt strength of more than 5.8cN and a v30 melt extensibility of more than 200 mm/s.

Description

There is the film of low OCS gel index

Technical field

The polypropene composition providing and have high fondant-strength and low OCS gel index is provided.In addition, the invention still further relates to a kind of polypropene composition with low OCS gel index and high solution intensity (HMS) of correspondence.

Background technology

High melt strength, propylene (HMS-PP) composition is well known in the art.But a challenge in existing HMS-PP is the film quality of its change.Film quality is represented by gel index, and the gel index OCS gel checking tool described in WO 2008/022802 is measured.

In addition, as known in the art, usually additive is added plastic material to improve its performance.The example of typical additive is, such as antioxidant or pigment etc.Usually these additives are added plastic matrix material with the form of additive agent mixture additive being mixed into a small amount of polymer powder.Additive agent mixture is sometimes also referred to as masterbatch.A small amount of polymer powder for additive agent mixture feeds when HMS end of processing usually.But the contribution of the final gel index of this additive agent mixture is usually out in the cold.In addition also do not recognize up to now, the molecular weight of the matrix polymer powder in the preparation of high melt strength, propylene (HMS-PP) also has great effect to final optical property.

Borealis describes the basis of Borealis high fondant-strength (HMS) post-reactor process at the EP 0879830 that 1997 submit to, wherein uses superoxide and divinyl to prepare long chain branch polypropylene (LCB-PP) material.This patent comprises powder melt flow rate (MFR) (MFR) and the granularity of wide region.But, this patent do not illustrate matrix polymer type and for the preparation of the polypropylene powder foot couple HMS quality of additive agent mixture, the impact of OCS film quality that particularly represented by gel index.

This area still needs a kind of method prepared reliably and/or carry high-quality HMS-PP.

Summary of the invention

Therefore, an object of the present invention is to provide and a kind ofly technician can be made to prepare polypropene composition and a kind of film with low-gel content prepared by this polypropene composition.

The present inventor surprisingly finds now, and final gel index is by increasing matrix polymer and significantly reducing for the MFR of the optional polypropylene powder of additive agent mixture.

Therefore, the present invention relates to a kind of method that polypropene composition is provided, described polypropene composition comprises branched polypropylene (b-PP), as at least 90 % by weight branched polypropylene (b-PP), described method at least comprises: step (a), polypropylene (PP) and thermolysis free radical forming agent and optional difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer is wherein made to react, obtain described branched polypropylene (b-PP) thus

Wherein

The melt flow rate (MFR) MFR of (a) described polypropylene (PP) ₂(230 DEG C) be greater than 1.0g/10min, preferably in 1.0 to 13.0g/10min scope, as in 3.0 to 13g/10min scope;

B () described polypropene composition and/or described branched polypropylene (b-PP) have the F being greater than 5.8cN ₃₀melt strength and the v being greater than 200mm/s ₃₀melt extensibility, wherein said F ₃₀melt strength and described v ₃₀melt extensibility is measured according to ISO16790:2005.

The present invention further provides a kind of polypropene composition, comprising:

(a) at least 90 weight part, as 95 to 99 weight part branched polypropylene (b-PP); With

(b) 1 to 5 melt flow rate (MFR) MFR of measuring according to ISO 1133 of weight part ₂(230 DEG C) polypropylene in 1.0 to 18.0g/10min scope (PP '),

Wherein said polypropene composition has

-in 7.0 to 13.0g/10min scope according to ISO 1133 measure melt flow rate (MFR) MFR ₂(230 DEG C), and

-be less than 1,000, be preferably less than 800 gel index;

And wherein described polypropene composition and/or described branched polypropylene (b-PP) have further

-F in 5.8 to 13.0cN scope, preferably in 6.0 to 12.5cN scope, more preferably in 6.0 to 12.0cN scope ₃₀melt strength, and

-v in 210 to 300mm/s scope ₃₀melt extensibility,

Wherein said F ₃₀melt strength and described v ₃₀melt extensibility is measured according to ISO 16790:2005.

Below in more detail the present invention is described.

First the independent component used in the present invention is described, that is: polypropylene (PP), as linear polypropylene (l-PP '); Polypropylene (PP '), as linear polypropylene (l-PP '); Branched polypropylene (b-PP); With additive (A) and polypropene composition.The method of protection is described subsequently in more detail.But if mention independent component and polypropene composition respectively, any information or any preferred embodiment that are provided for independent component or polypropene composition are also applicable to method of the present invention.

Branched polypropylene (b-PP)

Be branched polypropylene (b-PP) according to the main ingredient of polypropene composition provided by the invention.The difference of branched polypropylene and linear polypropylene is that polypropylene backbone comprises side chain, but not branched polypropylene (i.e. linear polypropylene) does not comprise side chain.Side chain has great effect to polyacrylic rheology.Therefore, linear polypropylene and branched polypropylene are clearly distinguished by its flowing property under stress.

Branching reaches by using special catalyst (i.e. specific single-site catalysts) or chemical modification.About the preparation of the branched polypropylene using special catalyst to obtain, with reference to EP 1 892 264.About the branched polypropylene obtained by chemical modification, with reference to EP 0 879 830 A1.In this case, branched polypropylene is also referred to as high melt strength, propylene.Obtained by following chemical modification in greater detail according to branched polypropylene of the present invention (b-PP), and be therefore high melt strength, propylene (HMS-PP).Therefore, term " branched polypropylene (b-PP) " and " high melt strength, propylene (HMS-PP) " can be considered to synonym in the present invention.

Therefore, the branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) as the main ingredient of polypropene composition has the F being greater than 5.8cN ₃₀melt strength and the v being greater than 200mm/s ₃₀melt extensibility, preferably has being greater than the F in 5.8 to 20.0cN scope ₃₀melt strength and being greater than the v in 200 to 300mm/s scope ₃₀melt extensibility, to provide the polypropene composition of the generation with good shear-thinning property.F ₃₀melt strength and v ₃₀melt extensibility is measured according to ISO 16790:2005.

Typically, polypropene composition of the present invention has the F being greater than 5.8cN ₃₀melt strength and the v being greater than 200mm/s ₃₀melt extensibility, preferably has being greater than the F in 5.8 to 20.0cN scope ₃₀melt strength and being greater than the v in 200 to 300mm/s scope ₃₀melt extensibility.

In a preferred embodiment, branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) has

(a) be greater than 5.8cN, as being greater than in 5.8 to 20.0cN scope, more preferably greater than 6.0cN, also will more preferably in 6.0 to 18.0cN scope, more more preferably in 6.2 to 15.0cN scope, also will more more preferably in 6.0 to 13.0cN scope or in 6.2 to 13.0cN scope, most preferably in 6.0 to 12.0cN scope or in 6.5 to 12.0cN scope, as the F in 6.6 to 12.0cN scope or in 6.6 to 11.5cN scope ₃₀melt strength;

With

(b) being greater than in 210 to 300mm/s scope, as being greater than in 220 to 300mm/s scope, more preferably greater than 225mm/s, also will v more preferably in 225 to 300mm/s scope, more more preferably in 230 to 290mm/s scope ₃₀melt extensibility.

In a particularly preferred embodiment, branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) has the F being greater than 5.8cN ₃₀melt strength and being greater than the v in 210 to 300mm/s scope ₃₀melt extensibility, as being greater than the F in 5.8 to 20.0cN scope ₃₀melt strength and being greater than the v in 220 to 300mm/s scope ₃₀melt extensibility, more preferably greater than the F of 6.0cN ₃₀melt strength and the v being greater than 225mm/s ₃₀melt extensibility, also will F more preferably in 6.0 to 18.0cN scope ₃₀melt strength and the v in 225 to 300mm/s scope ₃₀melt extensibility, then the F more preferably in 6.2 to 15.0cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility, also will F more preferably in 6.2 to 13.0cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility, the F most preferably in 6.0 to 12.0cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility, as the F in 6.6 to 11.5cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility.

In addition or alternatively, branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) can be limited further by strain hardening coefficient (SHF).Therefore, preferably, branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) is at 3.0s ^-1strain rate and 2.5 the lower strain hardening coefficient (SHF) measured of prosperous base strain be at least 1.7, more preferably at least 1.9, more more preferably in 1.9 to 7.0 scopes, also will more preferably in 1.9 to 6.5 scopes.

In addition, preferably, the melt flow rate (MFR) MFR measured according to ISO 1133 of this branched polypropylene (b-PP) (preferred high melt strength, propylene (HMS-PP)) ₂(230 DEG C) be at least 2.0g/10min, more preferably in 2.0 to 40.0g/10min scope, also will more preferably in 4.0 to 30.0g/10min scope, more more preferably in 5.0 to 20.0g/10min scope, as in 7.0 to 13.0g/10min scope, as in 8.0 to 12.0g/10min scope.

Therefore, In a particular embodiment, branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) has

(a) at least 2.0g/10min, preferably in 2.0 to 40.0g/10min scope, more preferably in 4.0 to 30.0g/10min scope, also will more preferably in 5.0 to 20.0g/10min scope, more more preferably in 7.0 to 13.0g/10min scope, as the melt flow rate (MFR) MFR in 8.0 to 12.0g/10min scope ₂(230 DEG C);

(b) be greater than 5.8cN, as being greater than in 5.8 to 20.0cN scope, more preferably greater than 6.0cN, also will more preferably in 6.0 to 18.0cN scope, more more preferably in 6.2 to 15.0cN scope, also will more more preferably in 6.0 to 13.0cN scope or in 6.2 to 13.0cN scope, most preferably in 6.0 to 12.0cN scope or in 6.5 to 12.0cN scope, as the F in 6.6 to 12.0cN scope or in 6.6 to 11.5cN scope ₃₀melt strength; With

(c) being greater than in 210 to 300mm/s scope, as being greater than in 220 to 300mm/s scope, more preferably greater than 225mm/s, also will v more preferably in 225 to 300mm/s scope, more more preferably in 230 to 290mm/s scope ₃₀melt extensibility.

Therefore, in a particular embodiment, branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) has the melt flow rate (MFR) MFR of at least 2.0g/10min ₂(230 DEG C), be greater than the F of 5.8cN ₃₀melt strength and being greater than the v in 210 to 300mm/s scope ₃₀melt extensibility, as the melt flow rate (MFR) MFR in 2.0 to 40.0g/10min scope ₂(230 DEG C), being greater than the F in 5.8 to 20.0cN scope ₃₀melt strength and being greater than the v in 220 to 300mm/s scope ₃₀melt extensibility, the melt flow rate (MFR) MFR more preferably in 4.0 to 30.0g/10min scope ₂(230 DEG C), be greater than the F of 6.0cN ₃₀melt strength and the v being greater than 225mm/s ₃₀melt extensibility, also will melt flow rate (MFR) MFR more preferably in 5.0 to 20.0g/10min scope ₂(230 DEG C), F in 6.0 to 18.0cN scope ₃₀melt strength and the v in 225 to 300mm/s scope ₃₀melt extensibility, then the melt flow rate (MFR) MFR more preferably in 7.0 to 13.0g/10min scope ₂(230 DEG C), F in 6.2 to 15.0cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility, also will melt flow rate (MFR) MFR more more preferably in 6.2 to 13.0g/10min scope ₂(230 DEG C), F in 6.2 to 13.0cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility, the melt flow rate (MFR) MFR most preferably in 8.0 to 12.0g/10min scope ₂(230 DEG C), F in 6.0 to 12.0cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility, as the melt flow rate (MFR) MFR in 7.0 to 13.0g/10min scope ₂(230 DEG C), F in 6.6 to 11.5cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility.

Preferably, the fusing point of branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) be at least 130 DEG C, more preferably at least 135 DEG C and most preferably at least 140 DEG C.Tc is preferably at least 110 DEG C, more preferably at least 120 DEG C.

In addition, branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) can be side chain atactic propene copolymer (b-R-PP) (i.e. high fondant-strength atactic propene copolymer (R-HMS-PP)) or side chain alfon (b-H-PP) (i.e. high fondant-strength alfon (H-HMS-PP)), and the latter is preferred.

For the purposes of the present invention, word " alfon " refers to substantially the polypropylene that (namely at least 97 % by mole, preferably at least 98 % by mole, more preferably at least 99 % by mole, most preferably at least 99.8 % by mole) are made up of propylene units.In a preferred embodiment, in alfon, only propylene units can be detected.

When branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) is for side chain atactic propene copolymer (b-R-PP) (i.e. high fondant-strength atactic propene copolymer (R-HMS-PP)), it comprises the monomer copolymerizable with propylene, such as comonomer, such as ethene and/or C ₄to C ₁₂alpha-olefines, particularly ethene and/or C ₄to C ₁₀alpha-olefines, such as 1-butylene and/or 1-hexene.Preferably, side chain atactic propene copolymer (b-R-PP) (i.e. high fondant-strength atactic propene copolymer (R-HMS-PP)) comprises the monomer copolymerizable with propylene, particularly be made up of the monomer copolymerizable with propylene, the group that the described monomer copolymerizable with propylene selects free ethylene, 1-butylene and 1-hexene to form.More preferably, side chain atactic propene copolymer (b-R-PP) (i.e. high fondant-strength atactic propene copolymer (R-HMS-PP)) also comprises the unit of derived from ethylene and/or 1-butylene except propylene.In a preferred embodiment, side chain atactic propene copolymer (b-R-PP) (i.e. high fondant-strength atactic propene copolymer (R-HMS-PP)) comprises the unit of only derived from ethylene and propylene.The co-monomer content of side chain atactic propene copolymer (b-R-PP) (i.e. high fondant-strength atactic propene copolymer (R-HMS-PP)) preferably more preferably will be greater than 0.5 % by mole within the scope of 7.0 % by mole within the scope of 10.0 % by mole, also being greater than 0.2 % by mole.

On this point, it should be mentioned that the high melt strength, propylene (HMS-PP) for high fondant-strength alfon (H-HMS-PP) or high fondant-strength atactic propene copolymer (R-HMS-PP) can comprise the unsaturated monomer different from the comonomer being defined for high fondant-strength atactic propene copolymer (R-HMS-PP) in addition.In other words, high fondant-strength alfon (H-HMS-PP) or high fondant-strength atactic propene copolymer (R-HMS-PP) can comprise and propylene, ethene and other C ₄to C ₁₂the unsaturated unit that alpha-olefines is different, as difunctionality unsaturated monomer and/or the multifunctional unsaturated low-molecular weight polymer of following detailed restriction.Therefore, homopolymer and the actual unmodified polypropylene referred to for being obtained Melt strength polypropylene (HMS-PP) by the chemical modification of following detailed restriction of the copolymer based definition in high melt strength, propylene (HMS-PP), i.e. polypropylene (PP), preferred linear polypropylene (l-PP).

Therefore, in a preferred embodiment, branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) comprises

If a () branched polypropylene (b-PP) is high fondant-strength alfon (H-HMS-PP), derived from following unit

(i) propylene, and

(ii) difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer,

Or

If b () branched polypropylene (b-PP) is high fondant-strength atactic propene copolymer (R-HMS-PP), derived from following unit

(i) propylene

(ii) ethene and/or C ₄to C ₁₀alpha-olefines, such as 1-butylene and/or 1-hexene, optimal ethylene, and

(iii) difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer.

" difunctionality is unsaturated " that more than use or " multifunctional unsaturated " refers to preferably there are two or more non-aromatic double bonds, such as, in Vinylstyrene or cyclopentadiene or polyhutadiene.Only use preferably this difunctionality unsaturated compound polymerisable or multifunctional unsaturated compound (as follows) under the help of free radical.Unsaturated position reality under its chemical binding state of difunctionality unsaturated compound or multifunctional unsaturated compound is not " undersaturated ", because each double bond is used as the covalent linkage of the polymer chain of unmodified polypropylene (i.e. polypropylene (PP), preferably linear polypropylene (l-PP)).

Preferred number average molecular weight (M _n)≤10000g/mol, by a kind of and/or multiple unsaturated monomer and unmodified polypropylene (i.e. polypropylene (PP), preferred linear polypropylene (l-PP)) reaction of the difunctionality unsaturated monomer that synthesizes and/or multifunctional unsaturated low-molecular weight polymer carries out under the existence of hot radical forming agent (namely decomposing free radical forming agent, as hot decomposable asymmetric choice net superoxide).

Difunctionality unsaturated monomer can be

-divinyl compound, such as divinyl aniline, m-divinyl benzene, p-divinyl benzene, divinyl pentane and divinyl propane;

-allylic cpd, such as allyl acrylate, allyl methacrylate(AMA), toxilic acid allyl group methyl esters and allyl vinyl ether;

-dienes, such as 1,3-butadiene, chloroprene, cyclohexadiene, cyclopentadiene, 2,3-dimethylbutadienes, heptadiene, hexadiene, isoprene and Isosorbide-5-Nitrae-pentadiene;

The mixture of-aromatic series and/or two (maleimide) two (citraconimides) of aliphatics and these unsaturated monomers.

Particularly preferred difunctionality unsaturated monomer is 1,3-butadiene, isoprene, dimethylbutadiene and Vinylstyrene.

Preferred number average molecular weight (M _nthe multifunctional unsaturated low-molecular weight polymer of)≤10000g/mol can be synthesized by one or more unsaturated monomers.

The example of this low-molecular weight polymer is

-polybutadiene, in the different microstructures (i.e. Isosorbide-5-Nitrae-cis, Isosorbide-5-Nitrae-trans and 1,2-(vinyl)) particularly wherein in polymer chain, 1,2-(vinyl) configuration accounts for major part,

There is in-polymer chain the divinyl of 1,2-(vinyl) and cinnamic multipolymer.

Preferred low-molecular weight polymer is polyhutadiene, particularly has the polyhutadiene of the divinyl of 1,2-(vinyl) configuration being greater than 50.0 % by weight.

Branched polypropylene (i.e. high melt strength, propylene (HMS-PP)) can comprise more than a kind of difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer.Even more preferably difunctionality unsaturated monomer and the amount of multifunctional unsaturated low-molecular weight polymer in branched polypropylene (i.e. high melt strength, propylene (HMS-PP)) are in 0.01 % by weight to 10.0 % by weight scope based on branched polypropylene (i.e. high melt strength, propylene (HMS-PP)).

In a preferred embodiment, (namely high melt strength, propylene (HMS-PP) is not containing additive (A) for branched polypropylene (b-PP).Therefore, when polypropene composition of the present invention comprises additive (A), these additives (A) are not brought in polypropene composition in the preparation process of branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)).

Polypropylene (PP)

As mentioned above, branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) is for by making polypropylene (PP) and thermolysis free radical forming agent and optional difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer react the modified polypropene obtained.

Special aspects of the present invention is that particular modification polypropylene in the present invention must for the preparation of branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)), and therefore for the preparation of the polypropene composition comprising branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)).A special discovery is that polypropylene (PP) (preferred linear polypropylene (l-PP)) must have quite low molecular weight and therefore quite high melt flow rate (MFR).Therefore, preferably, the melt flow rate (MFR) MFR that measures according to ISO 1133 of polypropylene (PP) (preferred linear polypropylene (l-PP)) ₂(230 DEG C) be greater than 1.0g/10min, preferably being greater than in 1.0 to 18.0g/10min scope, as to be greater than in 1.0 to 15.0g/10min scope or being greater than in 1.1 to 15.0g/10min scope, more preferably being greater than in 1.2 to 15.0g/10min scope or in 1.5 to 15.0g/10min scope, also will more preferably in 2.0 to 15.0g/10min scope, more more preferably in 3.0 to 13.0g/10min scope.

In a particular embodiment, the melt flow rate (MFR) MFR that measures according to ISO 1133 of polypropylene (PP) (preferred linear polypropylene (l-PP)) ₂(230 DEG C) be greater than 1.0g/10min, preferably being greater than in 1.0 to 18.0g/10min scope, as to be greater than in 1.0 to 15.0g/10min scope or being greater than in 1.1 to 15.0g/10min scope, more preferably being greater than in 1.2 to 15.0g/10min scope or in 1.5 to 15.0g/10min scope, also will more preferably in 2.0 to 15.0g/10min scope, more more preferably in 3.0 to 13.0g/10min scope, prerequisite does not comprise value 10.0g/10min.

With the difference for its polypropylene prepared (PP), branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) is that the main chain of branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) comprises side chain, and initial product (i.e. polypropylene (PP)) does not comprise or comprises side chain hardly.Side chain has great effect to polyacrylic rheology.Therefore, the branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) of initial product (i.e. polypropylene (PP)) and acquisition is clearly distinguished by the flowing property under its stress.

In addition, as mentioned above, polypropylene (PP) is preferably linear polypropylene (l-PP).Identical consideration is applicable to the polypropylene (PP ') of following detailed description, and in a preferred embodiment, polypropylene (PP ') is also linear polypropylene (l-PP ').Therefore, in the present invention, term " linear polypropylene " refers to linear polypropylene, demonstrates and does not have branched structure or almost unbranched structure.Owing to there is not side chain, linear polypropylene (i.e. linear polypropylene (l-PP) and linear polypropylene (l-PP ')) preferred feature is low v ₃₀melt extensibility and/or low F ₃₀melt strength.

Therefore, preferably linear polypropylene (l-PP) has

A () is greater than 1.0cN, is preferably greater than 2.0cN, more preferably in 1.0 to 65cN scope, also will more preferably in 1.5 to 50cN scope, more more preferably in 2.0 to 50cN scope, also will more more preferably in 2.5 to 50cN scope, as the F in 2.5 to 30cN scope ₃₀melt strength;

With

(b) lower than 200mm/s, preferably lower than 190mm/s, more preferably 100 to lower than within the scope of 200mm/s, also will more preferably in 120 to 190mm/s scope, more more preferably in 120 to 175mm/s scope, as the v in 125 to 170mm/s scope ₃₀melt extensibility.

In other words, preferably, linear polypropylene (l-PP) has the F being greater than 1.0cN ₃₀melt strength and the v lower than 200mm/s ₃₀melt extensibility, is preferably greater than the F of 2.0cN ₃₀melt strength and the v lower than 190mm/s ₃₀melt extensibility, the F more preferably in 1.0 to 65cN scope ₃₀melt strength and 100 to lower than the v within the scope of 200mm/s ₃₀melt extensibility, F more more preferably in 2.0 to 50cN scope ₃₀melt strength and the v in 120 to 190mm/s scope ₃₀melt extensibility, also will F more more preferably in 2.5 to 50cN scope ₃₀melt strength and the v in 120 to 190mm/s scope ₃₀melt extensibility, as the F in 2.5 to 30cN scope ₃₀melt strength and the v in 120 to 175mm/s scope ₃₀melt extensibility.

Therefore, In a particular embodiment, linear polypropylene (l-PP) has

(a) be greater than 1.0g/10min, preferably being greater than in 1.0 to 18.0g/10min scope, as being greater than in 1.0 to 15.0g/10min scope, more preferably in 1.5 to 15.0g/10min scope, also will the melt flow rate (MFR) MFR measured according to ISO 1133 more preferably in 2.0 to 15.0g/10min scope, more more preferably in 3.0 to 13.0g/10min scope ₂(230 DEG C);

B () is greater than 1.0cN, is preferably greater than 2.0cN, more preferably in 1.0 to 65cN scope, also will more preferably in 1.5 to 50cN scope, more more preferably in 2.0 to 50cN scope, also will more more preferably in 2.5 to 50cN scope, as the F in 2.5 to 30cN scope ₃₀melt strength; With

(c) lower than 200mm/s, preferably lower than 190mm/s, more preferably 100 to lower than within the scope of 200mm/s, also will more preferably in 120 to 190mm/s scope, more more preferably in 120 to 175mm/s scope, as the v in 125 to 170mm/s scope ₃₀melt extensibility.

Therefore, In a particular embodiment, polypropylene (PP) has the melt flow rate (MFR) MFR being greater than 1.0g/10min for linear polypropylene (l-PP), this linear polypropylene (l-PP) ₂(230 DEG C), be greater than the F of 1.0cN ₃₀melt strength and the v lower than 200mm/s ₃₀melt extensibility, preferably being greater than the melt flow rate (MFR) MFR in 1.0 to 18.0g/10min scope ₂(230 DEG C), be greater than the F of 2.0cN ₃₀melt strength and the v lower than 190mm/s ₃₀melt extensibility, more preferably being greater than the melt flow rate (MFR) MFR in 1.0 to 15.0g/10min scope ₂(230 DEG C), F in 1.0 to 65cN scope ₃₀melt strength and 100 to lower than the v within the scope of 200mm/s ₃₀melt extensibility, more more preferably being greater than the melt flow rate (MFR) MFR in 1.5 to 15.0g/10min scope ₂(230 DEG C), F in 2.0 to 50cN scope ₃₀melt strength and the v in 120 to 190mm/s scope ₃₀melt extensibility, also will more more preferably being greater than the melt flow rate (MFR) MFR in 2.0 to 15.0g/10min scope ₂(230 DEG C), F in 2.5 to 50cN scope ₃₀melt strength and the v in 120 to 190mm/s scope ₃₀melt extensibility, as being greater than the melt flow rate (MFR) MFR in 3.0 to 13.0g/10min scope ₂(230 DEG C), F in 2.5 to 30cN scope ₃₀melt strength and the v in 120 to 175mm/s scope ₃₀melt extensibility.

Preferably, the fusing point of polypropylene (PP) (preferred linear polypropylene (l-PP)) be at least 140 DEG C, more preferably at least 150 DEG C and also will more preferably at least 158 DEG C.

In addition, preferably, polypropylene (PP) (preferred linear polypropylene (l-PP)) uses with the form of the particle of specific dimensions.It is therefore preferable that polypropylene (PP) (preferred linear polypropylene (l-PP)) has

(a) lower than 1,500 μm, more preferably less than 1,000 μm, also will more preferably 50 to lower than 1, within the scope of 000 μm, more more preferably within the scope of 100 to 800 μm, as the size-grade distribution d within the scope of 150 to 600 μm ₉₀;

And/or

(b) lower than 1,000 μm, more preferably less than 800 μm, also will more preferably 30 to lower than 1, within the scope of 000 μm, more more preferably within the scope of 50 to 600 μm, as the size-grade distribution d within the scope of 100 to 500 μm ₅₀;

And/or

(c) lower than 1.80, more preferably less than 1.75, also will more preferably less than 1.50, more more preferably in 1.00 to 1.75 scopes, also will d more more preferably in 1.10 to 1.50 scopes ₉₀/ d ₅₀ratio.

Polypropylene (PP) (preferred linear polypropylene (l-PP)) can (such as by using single-site catalysts or ziegler natta catalyst) preparation in a known way.Polypropylene (PP) (preferred linear polypropylene (l-PP)) can be alfon (H-PP) (preferred straight chain alfon (l-H-PP)) or propylene copolymer (R-PP) (preferred straight chain propylene copolymer (l-R-PP)).About co-monomer content and the type of comonomer, with reference to the information being provided for branched polypropylene (b-PP), particularly high fondant-strength atactic propene copolymer (R-HMS-PP) above.Preferably, polypropylene (PP) is linear polypropylene (l-PP).Also will more preferably, polypropylene (PP) is straight chain alfon (l-H-PP).Therefore, respectively about melt flow rate (MFR) MFR ₂(230 DEG C), fusing point, F ₃₀melt strength, v ₃₀the all information that melt extensibility and granularity and size-grade distribution provide is specially adapted to straight chain alfon (l-H-PP).

In a preferred embodiment, polypropylene (PP) (preferred linear polypropylene (l-PP)) is not containing additive (A).Therefore, when polypropene composition of the present invention comprises additive (A), these additives (A) are not brought in polypropene composition in the preparation process of branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)).

Polypropylene (PP ')

In the preparation process of polypropene composition of the present invention, another kind of polypropylene (PP ') can be added.This polypropylene (PP ') be preferred for bringing additive (A) into polypropene composition of the present invention.Another discovery of the present invention is, if by using specific polypropylene carrier to introduce additive (A), optical property (the i.e. low gel index) aspect of polypropene composition of the present invention obtains result good especially.Therefore, in a preferred embodiment, additive (A) introduces polypropene composition of the present invention with the form of additive agent mixture (AM), wherein this additive agent mixture comprises polypropylene (PP ') and additive (A), is preferably made up of polypropylene (PP ') and additive (A).

Preferably, polypropylene (PP ') is linear polypropylene (l-PP ').

More preferably, polypropylene (PP ') (i.e. linear polypropylene (PP ')) lower molecular weight and therefore quite high melt flow rate (MFR) must be had.Therefore, preferably, polypropylene (PP ') (preferred linear polypropylene (l-PP ')) the melt flow rate (MFR) MFR that measures according to ISO 1133 ₂(230 DEG C) be greater than 1.0g/10min, preferably being greater than in 1.0 to 18.0g/10min scope, as being greater than in 1.0 to 15.0g/10min scope, more preferably in 1.5 to 15.0g/10min scope, also will more preferably in 2.0 to 15.0g/10min scope, more more preferably in 3.0 to 13.0g/10min scope.

Preferably, polypropylene (PP ') (preferred linear polypropylene (l-PP ')) fusing point be at least 140 DEG C, more preferably at least 150 DEG C and also will more preferably at least 158 DEG C.

In addition, as mentioned above, polypropylene (PP ') is preferably linear polypropylene (l-PP ') and therefore demonstrates and do not have branched structure or be almost unbranched structure.Owing to there is not side chain, and linear polypropylene (l-PP ') preferably there is low v ₃₀melt extensibility and/or low F ₃₀the feature of melt strength.

It is therefore preferable that linear polypropylene (l-PP ') has

A () is greater than 1.0cN, is preferably greater than 2.0cN, more preferably in 1.0 to 65cN scope, also will more preferably in 1.5 to 50cN scope, more more preferably in 2.0 to 50cN scope, also will more more preferably in 2.5 to 50cN scope, as the F in 2.5 to 30cN scope ₃₀melt strength;

With

(b) lower than 200mm/s, preferably lower than 190mm/s, more preferably 100 to lower than within the scope of 200mm/s, also will more preferably in 120 to 190mm/s scope, more more preferably in 120 to 175mm/s scope, as the v in 125 to 170mm/s scope ₃₀melt extensibility.

In other words, preferably, linear polypropylene (l-PP ') has the F being greater than 1.0cN ₃₀melt strength and the v lower than 200mm/s ₃₀melt extensibility, is preferably greater than the F of 2.0cN ₃₀melt strength and the v lower than 190mm/s ₃₀melt extensibility, the F more preferably in 1.0 to 65cN scope ₃₀melt strength and 100 to lower than the v within the scope of 200mm/s ₃₀melt extensibility, then the F more preferably in 2.0 to 50cN scope ₃₀melt strength and the v in 120 to 190mm/s scope ₃₀melt extensibility, also will F more more preferably in 2.5 to 50cN scope ₃₀melt strength and the v in 120 to 190mm/s scope ₃₀melt extensibility, as the F in 2.5 to 30cN scope ₃₀melt strength and the v in 120 to 175mm/s scope ₃₀melt extensibility.

Therefore, In a particular embodiment, linear polypropylene (l-PP ') has

(a) be greater than 1.0g/10min, preferably being greater than in 1.0 to 18.0g/10min scope, as being greater than in 1.0 to 15.0g/10min scope, more preferably in 1.5 to 15.0g/10min scope, also will the melt flow rate (MFR) MFR measured according to ISO 1133 more preferably in 2.0 to 15.0g/10min scope, more more preferably in 3.0 to 13.0g/10min scope ₂(230 DEG C);

B () is greater than 1.0cN, is preferably greater than 2.0cN, more preferably in 1.0 to 65cN scope, also will more preferably in 1.5 to 50cN scope, more more preferably in 2.0 to 50cN scope, also will more more preferably in 2.5 to 50cN scope, as the F in 2.5 to 30cN scope ₃₀melt strength; With

(c) lower than 200mm/s, preferably lower than 190mm/s, more preferably 100 to lower than within the scope of 200mm/s, also will more preferably in 120 to 190mm/s scope, more more preferably in 120 to 175mm/s scope, as the v in 125 to 170mm/s scope ₃₀melt extensibility.

Therefore, In a particular embodiment, polypropylene (PP ') is linear polypropylene (l-PP '), and this linear polypropylene (l-PP ') there is the melt flow rate (MFR) MFR being greater than 1.0g/10min ₂(230 DEG C), be greater than the F of 1.0cN ₃₀melt strength and the v lower than 200mm/s ₃₀melt extensibility, preferably being greater than the melt flow rate (MFR) MFR in 1.0 to 18.0g/10min scope ₂(230 DEG C), be greater than the F of 2.0cN ₃₀melt strength and the v lower than 190mm/s ₃₀melt extensibility, more preferably being greater than the melt flow rate (MFR) MFR in 1.0 to 15.0g/10min scope ₂(230 DEG C), F in 1.0 to 65cN scope ₃₀melt strength and 100 to lower than the v within the scope of 200mm/s ₃₀melt extensibility, more excellent in being greater than the melt flow rate (MFR) MFR in 1.5 to 15.0g/10min scope ₂(230 DEG C), F in 2.0 to 50cN scope ₃₀melt strength and the v in 120 to 190mm/s scope ₃₀melt extensibility, also will more more preferably being greater than the melt flow rate (MFR) MFR in 2.0 to 15.0g/10min scope ₂(230 DEG C), F in 2.5 to 50cN scope ₃₀melt strength and the v in 120 to 190mm/s scope ₃₀melt extensibility, as being greater than the melt flow rate (MFR) MFR in 3.0 to 13.0g/10min scope ₂(230 DEG C), F in 2.5 to 30cN scope ₃₀melt strength and the v in 120 to 175mm/s scope ₃₀melt extensibility.

In addition, preferably, polypropylene (PP ') (preferred linear polypropylene (l-PP ')) use with the form of the particle of specific dimensions.Therefore, preferably, polypropylene (PP ') (preferred linear polypropylene (l-PP ')) have

(a) lower than 1,500 μm, more preferably less than 1,000 μm, also will more preferably 50 to lower than 1, within the scope of 000 μm, more more preferably within the scope of 100 to 800 μm, as the size-grade distribution d within the scope of 150 to 600 μm ₉₀;

And/or

(b) lower than 1,000 μm, more preferably less than 800 μm, also will more preferably 30 to lower than 1, within the scope of 000 μm, more more preferably within the scope of 50 to 600 μm, as the size-grade distribution d within the scope of 100 to 500 μm ₅₀;

And/or

(c) lower than 1.80, more preferably less than 1.75, also will more preferably less than 1.50, more more preferably in 1.00 to 1.75 scopes, also will d more more preferably in 1.10 to 1.50 scopes ₉₀/ d ₅₀ratio.

Polypropylene (PP ') (and preferred linear polypropylene (l-PP ')) can (such as by using single-site catalysts or ziegler natta catalyst) preparation in a known way.Polypropylene (PP ') (preferred linear polypropylene (l-PP ')) can be alfon (H-PP ') (preferred straight chain alfon (l-H-PP ')) or propylene copolymer (R-PP ') (preferred straight chain propylene copolymer (l-R-PP ')).About co-monomer content and the type of comonomer, with reference to the information being provided for branched polypropylene (b-PP) above, particularly with reference to high fondant-strength atactic propene copolymer (R-HMS-PP).Preferably, polypropylene (PP ') is linear polypropylene (l-PP ').Also will more preferably, polypropylene (PP ') is straight chain alfon (l-H-PP ').Therefore, respectively about melt flow rate (MFR) MFR ₂(230 DEG C), fusing point, F ₃₀melt strength, v ₃₀the all information that melt extensibility and granularity and size-grade distribution provide is specially adapted to straight chain alfon (l-H-PP ').

In a particular embodiment, polypropylene (PP) and polypropylene (PP ') are identical.Therefore, in a preferred embodiment, polypropylene (PP) and polypropylene (PP ') are for having same nature (particularly above-mentioned melt flow rate (MFR) MFR ₂(230 DEG C), F ₃₀melt strength and v ₃₀melt extensibility) straight chain alfon, i.e. straight chain alfon (l-H-PP) and straight chain alfon (l-H-PP ').

As mentioned above, additive (A) is introduced polypropene composition as carrier by polypropylene (PP ').In other words, the additive agent mixture (AM) comprising polypropylene (PP ') and additive (A), the additive agent mixture (AM) be preferably made up of polypropylene (PP ') and additive (A) is used in for the preparation of the inventive method of polypropene composition.

Additive (A) can be any additive useful in the technical field of high melt strength, propylene (HMS-PP) and its application.Therefore in polypropene composition of the present invention to be used and therefore form be that the additive (A) of additive agent mixture (AM) includes but not limited to stablizer, such as antioxidant (such as, space Hinered phenols, phosphorous acid esters/phosphiinic acid ester, sulphur-containing antioxidant, alkyl scavenging agent, aromatic amine, hindered amine stabilizer or its blend), metal passivator (such as Irganox MD 1024) or UV stablizer (such as hindered amine as light stabilizer).Other typical additives are properties-correcting agent, such as static inhibitor or antifogging agent (such as ethoxylated amines and amides or glyceride type), acid scavenger (such as calcium stearate), whipping agent, caking agent (such as poly-isobutene), lubricant and resin (ionic polymer wax class, PE-and ethylene copolymer wax class, Fischer-Tropsch wax class, based on the wax class of Montan, compound or paraffin class based on fluorine), nucleator (such as talcum, benzoate, based on the compound of phosphorus, Sorbitol Powder, based on the compound of promise Buddhist nun alcohol (nonitol) or the compound based on acid amides), and surface slip agent and release agent (such as erucicamide, oleylamide, talcum native silicon dioxide and synthetic silica, or zeolites).Preferably, additive (A) is selected from the group of following formation: antioxidant (such as space Hinered phenols, phosphorous acid esters/phosphiinic acid ester, sulphur-containing antioxidant, alkyl scavenging agent, aromatic amine, hindered amine stabilizer or its blend), metal passivator (such as Irganox MD 1024) or UV stablizer (such as hindered amine as light stabilizer), static inhibitor or antifogging agent (such as ethoxylated amines and amides, or glyceride type), acid scavenger (such as calcium stearate), whipping agent, caking agent (such as poly-isobutene), lubricant and resin (ionic polymer wax class, PE-and ethylene copolymer wax class, Fischer-Tropsch wax class, based on the wax class of Montan, based on the compound of fluorine, or paraffin class), nucleator (such as talcum, benzoates, based on the compound of phosphorus, Sorbitol Powder, based on the compound of promise Buddhist nun alcohol, or based on the compound of acid amides), surface slip agent, release agent (such as erucicamide, oleylamide, talcum native silicon dioxide and synthetic silica, or zeolites) and its mixture.

Typically, the total amount based on additive agent mixture (AM) gross weight of additive (A) is not more than 25 % by weight, more preferably no more than 20 % by weight, as in 5 to 20 % by weight scopes in additive agent mixture (AM).

Polypropene composition

As mentioned above, due to method of the present invention, obtain the polypropene composition comprising branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)).In a preferred embodiment, polypropene composition of the present invention comprises branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) and polypropylene (PP ') (preferred linear polypropylene (l-PP ')) and optional at least one additive (A).

Main ingredient in polypropene composition of the present invention is branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)).Therefore, polypropene composition comprise at least 70 % by weight, more preferably at least 75 % by weight, more more preferably at least 80 % by weight, also will more preferably at least 85 % by weight, also will branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) more more preferably at least 90 % by weight, as at least 95 % by weight.

More preferably, polypropene composition of the present invention comprises

(a) branched polypropylene within the scope of 80 to 99 weight parts, preferably within the scope of 90 to 99 weight parts, more preferably within the scope of 95 to 99 weight parts (b-PP), preferred high melt strength, propylene (HMS-PP); With

(b) polypropylene within the scope of 1 to 20 weight part, preferably within the scope of 1 to 10 weight part, more preferably within the scope of 1 to 5 weight part (PP '), preferred linear polypropylene (l-PP ').

In a preferred embodiment, branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) and polypropylene (PP ') (preferred linear polypropylene (l-PP ')) for only having polymeric constituent in polypropene composition.In other words, polypropene composition can comprise the additive (A) that more than at least one limits more in detail in addition, but the amount do not comprised based on the gross weight of polypropene composition more than 5 % by weight, more preferably above 2 % by weight, also will more preferably above other polymkeric substance of 1 % by weight.In a particular embodiment, polypropene composition is by branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)), polypropylene (PP ') (preferred linear polypropylene (l-PP ')) and at least one additive (A) form.

Preferably, in polypropene composition, the total amount of the gross weight based on polypropene composition of additive (A) is not more than 5.0 % by weight, more preferably no more than 1.0 % by weight, as in 0.005 % by weight to 0.5 % by weight scope.

Therefore, method of the present invention relates to a kind of preparation of polypropene composition, and this polypropene composition comprises

(a) branched polypropylene within the scope of 80 to 99 weight parts, preferably within the scope of 90 to 99 weight parts, more preferably within the scope of 95 to 99 weight parts (b-PP), i.e. high melt strength, propylene (HMS-PP);

(b) melt flow rate (MFR) MFR measured according to ISO 1133 within the scope of 1 to 20 weight part, preferably within the scope of 1 to 10 weight part, more preferably within the scope of 1 to 5 weight part ₂(230 DEG C) in 1.0 to 18.0g/10min scope, preferably in 1.0 to 15.0g/10min scope, more preferably in 1.5 to 15.0g/10min scope, more more preferably in 2.0 to 15.0g/10min scope, as the polypropylene (PP ') in 3.0 to 13.0 scopes, preferred linear polypropylene (l-PP '); With

(c) optional within the scope of 0.005 to 5.0 weight part, preferably within the scope of 0.005 to 2.0 weight part, more preferably within the scope of 0.05 to 1.0 weight part, as the additive (A) within the scope of 0.05 to 0.5 weight part, wherein this additive (A) is preferably selected from the group of following formation: antioxidant, metal passivator, UV stablizer, static inhibitor, antifogging agent, acid scavenger, whipping agent, caking agent, lubricant, nucleator, surface slip agent, release agent and its mixture.

As mentioned above, branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) is the major portion in polypropene composition of the present invention.Therefore, preferably, final polypropene composition demonstrates the rheology similar to the rheology of branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)).

Therefore, polypropene composition of the present invention has

(a) be greater than 5.8cN, as being greater than in 5.8 to 20.0cN scope, more preferably greater than 6.0cN, also will more preferably in 6.0 to 18.0cN scope, more more preferably in 6.2 to 15.0cN scope, also will more more preferably in 6.0 to 13.0cN scope or in 6.2 to 13.0cN scope, most preferably in 6.0 to 12.0cN scope or in 6.5 to 12.0cN scope, as the F in 6.6 to 12.0cN scope or in 6.6 to 11.5cN scope ₃₀melt strength;

With

(b) being greater than in 210 to 300mm/s scope, as being greater than in 220 to 300mm/s scope, more preferably greater than 225mm/s, also will v more preferably in 225 to 300mm/s scope, more more preferably in 230 to 290mm/s scope ₃₀melt extensibility.

In a particularly preferred embodiment, polypropene composition of the present invention has the F being greater than 5.8cN ₃₀melt strength and being greater than the v in 210 to 300mm/s scope ₃₀melt extensibility, as being greater than the F in 5.8 to 20.0cN scope ₃₀melt strength and being greater than the v in 220 to 300mm/s scope ₃₀melt extensibility, more preferably greater than the F of 6.0cN ₃₀melt strength and the v being greater than 225mm/s ₃₀melt extensibility, also will F more preferably in 6.0 to 18.0cN scope ₃₀melt strength and the v in 225 to 300mm/s scope ₃₀melt extensibility, then the F more preferably in 6.2 to 15.0cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility, also will F more more preferably in 6.2 to 13.0cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility, the F most preferably in 6.0 to 12.0cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility, as the F in 6.6 to 11.5cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility.

In addition or alternatively, polypropene composition of the present invention can be limited by strain hardening coefficient (SHF).Therefore, preferably, polypropene composition of the present invention is at 3.0s ^-1strain rate and 2.5 the lower strain hardening coefficient (SHF) measured of prosperous base strain be at least 1.7, more preferably at least 1.9, more more preferably in 1.9 to 7.0 scopes, also will more preferably in 1.9 to 6.5 scopes.

In addition, preferably, the melt flow rate (MFR) MFR measured according to ISO 1133 of polypropene composition of the present invention ₂(230 DEG C) be at least 2.0g/10min, more preferably in 2.0 to 40.0g/10min scope, also will more preferably in 4.0 to 30.0g/10min scope, more more preferably in 5.0 to 20.0g/10min scope, as in 7.0 to 13.0g/10min scope, as in 8.0 to 12.0g/10min scope.

Therefore, In a particular embodiment, polypropene composition of the present invention has

(a) at least 2.0g/10min, preferably in 2.0 to 40.0g/10min scope, more preferably in 4.0 to 30.0g/10min scope, also will more preferably in 5.0 to 20.0g/10min scope, more more preferably in 7.0 to 13.0g/10min scope, as the melt flow rate (MFR) MFR in 8.0 to 12.0g/10min scope ₂(230 DEG C);

(b) be greater than 5.8cN, as being greater than in 5.8 to 20.0cN scope, more preferably greater than 6.0cN, also will more preferably in 6.0 to 18.0cN scope, more more preferably in 6.2 to 15.0cN scope, also will more more preferably in 6.0 to 13.0cN scope or in 6.2 to 13.0cN scope, most preferably in 6.0 to 12.0cN scope or in 6.5 to 12.0cN scope, as the F in 6.6 to 12.0cN scope or in 6.6 to 11.5cN scope ₃₀melt strength; With

(c) being greater than in 210 to 300mm/s scope, as being greater than in 220 to 300mm/s scope, more preferably greater than 225mm/s, also will v more preferably in 225 to 300mm/s scope, more more preferably in 230 to 290mm/s scope ₃₀melt extensibility.

Therefore, in embodiment more specifically, polypropene composition of the present invention has the melt flow rate (MFR) MFR of at least 2.0g/10min ₂(230 DEG C), be greater than the F of 5.8cN ₃₀melt strength and being greater than the v in 210 to 300mm/s scope ₃₀melt extensibility, as the melt flow rate (MFR) MFR in 2.0 to 40.0g/10min scope ₂(230 DEG C), being greater than the F in 5.8 to 20.0cN scope ₃₀melt strength and being greater than the v in 220 to 300mm/s scope ₃₀melt extensibility, the melt flow rate (MFR) MFR more preferably in 4.0 to 30.0g/10min scope ₂(230 DEG C), be greater than the F of 6.0cN ₃₀melt strength and the v being greater than 225mm/s ₃₀melt extensibility, also will melt flow rate (MFR) MFR more preferably in 5.0 to 20.0g/10min scope ₂(230 DEG C), F in 6.0 to 18.0cN scope ₃₀melt strength and the v in 225 to 300mm/s scope ₃₀melt extensibility, then the melt flow rate (MFR) MFR more preferably in 7.0 to 13.0g/10min scope ₂(230 DEG C), F in 6.2 to 15.0cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility, also will melt flow rate (MFR) MFR more more preferably in 6.2 to 13.0g/10min scope ₂(230 DEG C), F in 6.2 to 13.0cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility, the melt flow rate (MFR) MFR most preferably in 8.0 to 12.0g/10min scope ₂(230 DEG C), F in 6.0 to 12.0cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility, as the melt flow rate (MFR) MFR in 7.0 to 13.0g/10min scope ₂(230 DEG C), F in 6.6 to 11.5cN scope ₃₀melt strength and the v in 230 to 290mm/s scope ₃₀melt extensibility.

An important discovery of the present invention is, polypropene composition of the present invention and the film therefore prepared by this polypropene composition (limiting particularly) demonstrate the OCS gel index of reduction.Therefore preferably, the OCS gel index of polypropene composition of the present invention is less than 1,000, be preferably less than 800, be more preferably less than 500, also will more preferably in 5 to 800 scopes, more more preferably in 10 to 300 scopes, also will more more preferably in 10 to 200 scopes.

The above information provided is provided, such as, the present invention includes and there is following polypropene composition

(a) branched polypropylene within the scope of 80 to 99 weight parts, preferably within the scope of 90 to 99 weight parts, more preferably within the scope of 95 to 99 weight parts (b-PP) (i.e. high melt strength, propylene (HMS-PP));

(b) melt flow rate (MFR) MFR measured according to ISO 1133 within the scope of 1 to 20 weight part, preferably within the scope of 1 to 10 weight part, more preferably within the scope of 1 to 5 weight part ₂(230 DEG C) in 1.0 to 18.0g/10min scope, preferably in 1.0 to 15.0g/10min scope, more preferably in 1.5 to 15.0g/10min scope, more more preferably in 2.0 to 15.0g/10min scope, as the polypropylene (PP ') (preferred linear polypropylene (l-PP ') in 3.0 to 13.0 scopes); With

(c) optional within the scope of 0.005 to 5.0 weight part, preferably within the scope of 0.005 to 2.0 weight part, more preferably within the scope of 0.05 to 1.0 weight part, as the additive (A) within the scope of 0.05 to 0.5 weight part, wherein this additive (A) is preferably selected from the group of following formation: antioxidant, metal passivator, UV stablizer, static inhibitor, antifogging agent, acid scavenger, whipping agent, caking agent, lubricant, nucleator, surface slip agent, release agent and its mixture;

Wherein polypropene composition has

-at least 2.0g/10min, preferably in 2.0 to 40.0g/10min scope, more preferably in 4.0 to 30.0g/10min scope, also will more preferably in 5.0 to 20.0g/10min scope, more more preferably in 7.0 to 13.0g/10min scope, as the melt flow rate (MFR) MFR in 8.0 to 12.0g/10min scope ₂(230 DEG C); With

-be less than 1,000, be preferably less than 800, be more preferably less than 500, also will more preferably in 5 to 800 scopes, more more preferably in 10 to 300 scopes, also will OCS gel index more more preferably in 10 to 200 scopes;

And wherein polypropene composition and/or branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) have

-be greater than 5.8cN, as being greater than in 5.8 to 20.0cN scope, more preferably greater than 6.0cN, also will more preferably in 6.0 to 18.0cN scope, more more preferably in 6.2 to 15.0cN scope, also will more more preferably in 6.0 to 13.0cN scope or in 6.2 to 13.0cN scope, most preferably in 6.0 to 12.0cN scope or in 6.5 to 12.0cN scope, as the F in 6.6 to 12.0cN scope or in 6.6 to 11.5cN scope ₃₀melt strength; With

-being greater than in 210 to 300mm/s scope, as being greater than in 220 to 300mm/s scope, more preferably greater than 225mm/s, also will v more preferably in 225 to 300mm/s scope, more more preferably in 230 to 290mm/s scope ₃₀melt extensibility.

Film

As mentioned above, the invention still further relates to the film of the polypropene composition described in a kind of the application of comprising.Preferably, this film is cast film or blown film.Film also can be biaxially oriented film, as diaxial orientation blown film.Difference between this film is known to technician.This respect reference " Polypropylene Handbook ", the 405 to 414 page, the 2nd edition, Nello Pasquini (Ed.), Hanser.Preferably, film comprise at least 70 % by weight, more preferably at least 80 % by weight, more preferably at least 90 % by weight, more more preferably at least 95 % by weight according to polypropene composition of the present invention.In a preferred embodiment, this film is made up of polypropene composition of the present invention.

Method

An importance of the present invention is to use polypropylene (PP) (preferred linear polypropylene (l-PP)) preparation to comprise the polypropene composition of branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)).In other words, the present invention relates to the method that one provides the polypropene composition comprising branched polypropylene (b-PP), wherein the method at least comprises step (a), in step (a), make polypropylene (PP) and thermolysis free radical forming agent and optional difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer react, obtain branched polypropylene (b-PP) thus.Preferably, method of the present invention comprises another step (b) of then step (a), adds polypropylene (PP ') in step (b) in branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)).Even more preferably, method of the present invention comprises another step (b) of then step (a), adds the additive agent mixture (AM) comprising polypropylene (PP ') and additive (A) in step (b) in branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)).About definition and the preferred embodiment of polypropene composition, branched polypropylene (b-PP), polypropylene (PP), polypropylene (PP '), additive (A) and additive agent mixture (AM), with reference to the information provided above.

As mentioned above, in step (a), branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) obtains by using thermolysis free radical forming agent process polypropylene (PP) (preferred linear polypropylene (l-PP)).But, in this case, there is the excessive risk that harmful polypropylene (PP) (preferred linear polypropylene (PP)) is degraded.Therefore, preferably, chemical modification has been come as Chemical bond bridge unit by using difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer in addition.The proper method obtaining branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) is disclosed in such as EP 0 787 750, EP 0 879 830 A1 and EP 0 890 612 A2.In the application, All Files is incorporated to by reference.Therefore, the amount of thermolysis free radical forming agent (preferred superoxide) is preferably in 0.05 % by weight to 3.00 % by weight scope of the amount based on polypropylene (PP).Typical heat is decomposed free radical forming agent and add polypropylene (PP) (preferred linear polypropylene (l-PP)) together with difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer.But also possibility is not still more preferably:

First thermolysis free radical forming agent is added polypropylene (PP) (preferred linear polypropylene (l-PP)) by difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer subsequently,

Or it is contrary,

First difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer are added polypropylene (PP) (preferred linear polypropylene (l-PP)) by thermolysis free radical forming agent subsequently.

About for the preparation of the difunctionality unsaturated monomer of branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) and/or multifunctional unsaturated low-molecular weight polymer, with reference to " branched polypropylene " part.

As mentioned above, preferably, difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer use under the existence of thermolysis free radical forming agent.

Superoxide is preferred thermolysis free radical forming agent.Preferred thermolysis free radical forming agent is selected from the group of following formation: acyl peroxide, alkyl peroxide, hydroperoxide, peresters and peroxy carbonates.

Following superoxide is particularly preferred:

Acyl peroxide: benzoyl peroxide, peroxidation 4-chlorobenzoyl, peroxidation 3-methoxybenzoyl and/or methyl benzoyl.

Alkyl peroxide: allyl group tert-butyl peroxide, 2, 2-two (t-butylperoxy butane), 1, 1-bis(t-butylperoxy)-3, 3, 5-trimethyl-cyclohexane, 4, 4-bis(t-butylperoxy) n-butyl pentanoate, diisopropyl ammonia ylmethyl-t-amyl peroxy compound, dimethylamino methyl-t-amyl peroxy compound, Diethylaminomethyl-tert-butyl peroxide, dimethylamino methyl-tert-butyl peroxide, 1, 1-bis--(t-amyl peroxy) hexanaphthene, t-amyl peroxy compound, t-butylcumylperoxide, tert-butyl peroxide and/or 1-hydroxyl butyl normal-butyl superoxide.

Peresters and peroxy carbonates: butylperacetate, peracetic acid cumyl ester, perpropionic acid cumyl ester, peracetic acid cyclohexyl, cross hexanodioic acid di tert butyl carbonate, cross nonane diacid di tert butyl carbonate, cross pentanedioic acid di tert butyl carbonate, cross phthalic acid di tert butyl carbonate (di-t-butylperthalate), cross sebacic acid di tert butyl carbonate, perpropionic acid 4-nitro cumyl ester, peroxybenzoic acid 1-phenyl chlorocarbonate, styroyl nitro perbenzoate, two rings-(2,2,1) heptane percarboxylic acids tert-butyl ester, the 4-methoxycarbonyl perbutyric acid tert-butyl ester, the tetramethylene percarboxylic acids tert-butyl ester, the cyclohexyl peroxycarboxylic acid tert-butyl ester, the cyclopentyl percarboxylic acids tert-butyl ester, the cyclopropane percarboxylic acids tert-butyl ester, dimethyl crosses the styracin tert-butyl ester, 2-(2,2-diphenylacetylene) t-butylperoxyl benzoate, 4-methoxyl group t-butylperoxyl benzoate, t-butylperoxyl benzoate, tert-butyl carboxy hexanaphthene, cross the naphthoic acid tert-butyl ester, BPIC (t butyl peroxy isopropyl carbonate), cross the toluic acid tert-butyl ester, the 1-phenycyclopropyl percarboxylic acids tert-butyl ester, amylene-2-tert-butyl acrylate crossed by 2-propyl group, the 1-methylcyclopropyl groups percarboxylic acids tert-butyl ester, 4-nitrophenyl t-butyl peroxy-acetate, nitrophenyl peroxy t-butyl carbamate, the N-succinimido percarboxylic acids tert-butyl ester, cross the β-crotonic acid tert-butyl ester, the tertiary butyl crosses toxilic acid, cross Tert-butyl Methacrylate, cross octanoic acid ter-butyl ester, BPIC (t butyl peroxy isopropyl carbonate), t-butylperoxy isobutylate, cross tert-butyl acrylate and/or the perpropionic acid tert-butyl ester.

What also plan is the mixture of these free radical forming agents listed above.

Preferably, when polypropylene (PP) and the reaction between thermolysis free radical forming agent and optional difunctionality unsaturated monomer occurred at least 70%, preferably at least 80%, more more preferably at least 90%, as at least 95% or 99% time, start step (b) to obtain branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)).

In a preferred embodiment, step (a) and step (b) use forcing machine, such as twin screw extruder.

The special advantage of the use of forcing machine is, forcing machine can simultaneously for the preparation of side chain propylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)) with subsequently polypropylene (PP ') or additive agent mixture (AM) are added this side chain propylene (b-PP).In a preferred embodiment, in step (a), together with the thermolysis free radical forming agent (preferred superoxide) of polypropylene (PP) and foregoing detailed description and optional difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer, add forcing machine to provide branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)), difunctionality unsaturated monomer is selected from divinyl compound, allylic cpd or dienes.Forcing machine also may be used in the combination in pre-mixing device downstream, wherein difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer and thermolysis free radical forming agent are added the polypropylene in pre-mixing device.Subsequently, in step (b), preferably by polypropylene (PP ') (preferred linear polypropylene (l-PP ')) or based on this polypropylene (PP ') (being preferably based on this linear polypropylene (l-PP)), the additive agent mixture (AM) that comprises at least one additive (A) adds the downstream end of extruder screw not disturb the modified-reaction for providing branched polypropylene (b-PP) (i.e. high melt strength, propylene (HMS-PP)), as mentioned above.This respect, term " downstream end of extruder screw " is interpreted as in rear 60% of extruder screw length, preferably in rear 65% of extruder screw length, more preferably at least 70% of extruder screw length, as at least 75% of extruder screw.

Therefore, on direction of operating, preferably comprise opening for feed (FT), the first mixing region (MZ1), the second mixing region (MZ2) and mould (D) for forcing machine of the present invention (E), wherein side opening for feed (SFT) is positioned between the first mixing region (MZ1) and the second mixing region (MZ2).Preferably, forcing machine is screw extrusion press, as twin screw extruder.Therefore, by polypropylene (PP), thermolysis free radical forming agent (preferred superoxide) and optional difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer monomer (being preferably selected from divinyl compound, allylic cpd or dienes), but be not polypropylene (PP ') (be not namely linear polypropylene (l-PP ')) and be not additive (A), by opening for feed (FT) charging (preferably using feeder thus) to forcing machine and subsequently through downstream by the first mixing region (MZ1).Preferably, the degree of the shear-stress in the first mixing region (MZ1) is for making polypropylene (PP) be melted and starting with the chemical reaction of free radical forming agent and optional difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer.By polypropylene (PP ') (preferred linear polypropylene (l-PP ')) or additive agent mixture (AM) add the first mixing region (MZ1) after (namely between the first mixing region (MZ1) and the second mixing region (MZ2)), be namely fed to forcing machine.Preferably, polypropylene (PP ') (preferred linear polypropylene (l-PP ')) or additive agent mixture (AM) added by side opening for feed (SFT), preferably use side feeder thus.Subsequently, the all components of polypropene composition (comprise polypropylene (PP '), preferred linear polypropylene (l-PP ')) or additive agent mixture (AM) through downstream by the second mixing region (MZ2).Finally, polypropene composition is discharged by mould (D).

Preferably, the first mixing region (MZ1) is longer than the second mixing region (MZ2).Preferably, the length ratio [mm (MZ1)/mm (MZ2)] between the first mixing region (MZ1) and the second mixing region (MZ2) is at least 2/1, more preferably 3/1, more more preferably in 2/1 to 15/1 scope, also will more preferably in 3/1 to 10/1 scope.

The preparation of film has come with technology known in the art.Such as, film is by cast film or blown film technique preparation.In cast film technology, melt polypropylene composition is expressed on cold roller by slit extrusion die so that polymkeric substance is cooled to solid film.Typically, polypropene composition compresses first in an extruder and liquefies, and any additive may have been added polymkeric substance or introduced in this stage by masterbatch.Then make melts by flat film die (slit die), and extrusion film is taken off from one or more taking-up roller, in this process, extrusion film cooling and solidification.Verified this is conducive to the temperature of taking out roller (thus extrusion film cooled and solidification) to remain within the scope of 10 to 50 DEG C, preferably within the scope of 10 to 40 DEG C, more preferably within the scope of 12 to 35 DEG C.The product obtained is non-stretched film, if needed, it can by two-way stretch.

In blown film process, polypropene composition is extruded by ring mould and is tubular membrane by forming bubble (after solidification, bubble breaks between roll) blowing.Blowing is extruded and can be realized at the temperature preferably within the scope of 160 to 240 DEG C and cool by water or preferably by the blowing air of temperature within the scope of 10 to 50 DEG C (being generally air), to provide the frost line height of mould diameter 0.5 to 8 times.Blow-up ratio usually should in 1.5 to 4 scopes, such as in 2 to 4 scopes, preferably in 2.5 to 3.5 scopes.

Below, in more detail the present invention is described by example.

Embodiment

Example

A. measuring method

Unless limited otherwise, the definition of following term and measuring method are applicable to above general description of the present invention and following example.

Co-monomer content in polypropylene

Co-monomer content by after basic ownership, by quantitatively ¹³the quantitative Fourier transform infrared spectroscopy (FTIR) of C nucleus magnetic resonance (NMR) spectroscopic calibration measures with method well known in the art.Thin film to thickness is 250 μm and by spectrum with transmission mode record.

Particularly, the ethylene content of polypropylene ethylene multipolymer uses 720-722cm ^-1and 730-733cm ^-1the peak area of the baseline correction of the quantitative band that place finds measures.Propylene-1-butylene-multipolymer is at 767cm ^-1place's assessment.Quantitative result obtains based on the film thickness of reference.

Temperature of fusion (T _m) and melting heat (H _f), Tc (T _c) and heat of crystallization (H _c): measure 5mg to 10mg sample by Mettler TA820 dsc (DSC).DSC is according to ISO 3146/ 3rd part/method C2 with the circular flow of heating/cooling/heating, and scanning speed is 10 DEG C/min, and temperature range is within the scope of+23 DEG C to+210 DEG C.Tc and heat of crystallization (H _c) measured by cooling step, and temperature of fusion and melting heat (H _f) measured by second heating steps.

MFR ₂(230 DEG C) are measured according to ISO 1133 (230 DEG C, 2.16kg load).

Strain hardening coefficient (SHF)

Strain hardening coefficient is defined as

$\mathrm{SHF}=\frac{{\mathrm{\η}}_E^{+}(t,\stackrel{.}{\mathrm{\ϵ}})}{{\mathrm{\η}}_{\mathrm{LVE}}^{+}\left(t\right)}=\frac{{\mathrm{\η}}_E^{+}(t,\stackrel{.}{\mathrm{\ϵ}})}{{3\mathrm{\η}}^{+}\left(t\right)}$

Wherein

for uniaxial extension viscosity; With for the shear viscosity η of time-dependent manner in the linearity range of distortion ⁺(t) three times.

Use IRIS Rheo Hub 2008 measures the linear viscoelastic range in drawing process need by storage modulus and out-of-phase modulus data (G ', G " (ω)) calculate discrete relaxation time spectrum.Linear viscoelasticity data (G ', G " (ω)) by obtaining at 180 DEG C of lower frequency sweep measurement polypropylene or at 140 DEG C of lower frequency sweep measurement polyethylene with the Anton Paar MCR 300 being connected with 25mm parallel plate.Basic calculating principle for measuring discrete relaxation time spectrum is described in m, WinterHH, " Determination of the discrete relaxation and retardation time spectra from dynamicmechanical data ", in Rheol.Acta 28:511519 (1989), the document is all incorporated to the application by reference.

IRIS RheoHub 2008 relax time spectrum is expressed as N number of Maxwell pattern and

$\stackrel{o}{G}\left(t\right)=G_e\·\underset{1}{\overset{N}{\mathrm{\Σ}}}{g}_i{\·e}^{-\frac{t}{{\mathrm{\λ}}_i}}$

Wherein g _iand λ _ifor material parameter and G _efor equilibrium modulus.

The selection (N is for measuring discrete relaxation) of pattern maximum quantity realizes by using the option " optimization " from IRIS RheoHub 2008.Equilibrium modulus G _ebe set to zero.For obtaining nonlinear Quasi share IRIS Rheo Hub 2008 and use Doi-Edwards model to carry out.

Uniaxial extension viscosity obtain from the uniaxial extension flow measurement carried out at the Anton Paar MCR501 being connected with Sentmanat extensional fixture (SER-1).The temperature of uniaxial extension flow measurement is set to 180 DEG C, is used in 0.3s ^-1to 10s ^-1stretching (strain) speed in scope and cover the prosperous base range of strain of 0.3 to 3.0,

ε＝ln[(l–l ₀)/l ₀]，

L ₀for initial sample regular length and l is actual sample regular length.Special care is used for the preparation of the sample of extensional flow.At 230 DEG C, prepare sample by compression molded, then Slow cooling (not using forced water or air cooling) is to room temperature.

The method allows to obtain the sample not having the shape of unrelieved stress good.Before carrying out uniaxial extension flow measurement, sample is placed under test temperature several minutes to ensure thermostability (design temperature ± 0,1 DEG C).

F ₃₀melt strength and v ₃₀melt extensibility

ISO 16790:2005 is followed in the test that the application describes.

Strain-hardening property is according to document " Rheotens-Mastercurves and Drawability of Polymer Melts ", and M.H.Wagner, Polymer Engineering and Sience, the 36th volume, the method described in the 925 to 935 page measures.File content is incorporated to by reference.The strain hardenability of polymkeric substance by Rheotens device ( product, Siemensstr.2,74711Buchen, Germany) analyze, wherein molten thread elongates by pulling down with restriction acceleration.

Rheotens experimental simulation industrial spinning and extrusion.In principle, melts is suppressed by circular die or is extruded and draws the line generated.Stress on record extrudate is as the function of melt properties and measuring parameter (particularly exporting the measurement of ratio, particularly rate of extension between pulling speed).About the following result illustrated, material lab extruder HAAKEPolylab system is extruded with the toothed gear pump with cylindrical die (L/D=6.0/2.0mm).Be 5mm/s by the line rate of extrusion preconditioning of toothed gear pump, and melt temperature is set to 200 DEG C.Spinning threadling (spinline) length between mould and Rheotens take turns is 80mm.When experiment starts, the winding speed that Rheotens takes turns is adjusted to the speed (tension force is zero) of extruded polymer line: the winding speed then by being taken turns by Rheotens slowly increases and starts experiment, until polymer filament fracture.The acceleration of wheel is enough little, to measure tension force under quasi-stationary state.The acceleration of the melts line of leaving behind is 120mm/sec ².Rheotens and computer program EXTENS combination operation.EXTENS is Real time data acquisition program, and it shows and stores the take off data of tension force and drop-down speed.The end points of Rheotens curve (power is relative to pulley speed of rotation) is as F ₃₀melt strength and drawability value.

OCS gel index

1, equipment

Equipment forms by having the lab extruder ME 25/5200V1 of three heating zone, adapter and the wide mould of 150mm.Unit subsequently comprises: diameter 140mm, comprise the cold roller CR – 8 of Haake C40P heating and cooling device (15 DEG C to 90 DEG C); Line scan cameras FS-5/4096 pixel (daynamic transformation of gray level image); With there is the winder unit controlled up to the automatic tension of 10N.

2, for the distinctive setting of material of film preparation

Temperature for heating zone, cylinder place and mould arranges and classifies as following three groups to polypropylene according to MFR-scope:

Group 1:MFR-scope 0.3 to 2.0g/10min (230 DEG C/2.16kg), temperature 220/260/270/280/290 DEG C

Group 2:MFR-scope 2.0 to 10g/10min (230 DEG C/2.16kg), temperature 220/230/240/250/260 DEG C

Group 3:MFR-scope 10 to 33g/10min (230 DEG C/2.16kg), temperature 200/220/230/240/240 DEG C

Parameter preset:

Speed of rotation (screw rod): 30rpm

Pulling speed: 3m/min;

Film thickness is 50 μm

3, measure

After following parameter completes: when analogous material, in the cycle, approximately 60min runs; Very when differing materials, about 120min.

Target: regulate uniform thin film under constant melt pressure and melt temperature.Measured zone is standardized as 5m ².When region completes, measurement itself stops automatically.Simultaneously by printed report.

4, analyze

With reference to 1/m ², by finding that the number of defect is multiplied by quality coefficient according to size classes, add up to gel index.

Example:

Gel index=16.7

Granularity/size-grade distribution

Polymer sample is carried out classification test.Size test relates to the nested post of the sieve comprising the wire screen with following size: >20 μm, >32 μm, >63 μm, >100 μm, >125 μm, >160 μm, >200 μm, >250 μm, >315 μm, >400 μm, >500 μm, >710 μm, >1mm, >1.4mm, >2mm, >2.8mm.Sample is poured into the top sieve with maximum web opening.In post, each lower sifter device has the opening (size see above illustrate) less than last sieve.Base portion is receptor.Post is put into mechanical vibrator.Vibrator shakes this post.After vibration completes, the material on each sieve is weighed.Then by the weight of the sample of each sieve divided by gross weight to draw the percentage ratio of the sample that each sieve retains.

B, example

Linear polypropylene (l-PP)

L-PP1 is MFR ₂(230 DEG C) are 0.37g/10min, d ₅₀be 1,100 μm, d ₉₀be 1,650 μm, temperature of fusion Tm is 164 DEG C, F ₃₀melt strength is 68cN and v ₃₀melt extensibility is the straight chain alfon of 146mm/s.

L-PP2 is MFR ₂(230 DEG C) are 3.48g/10min, d ₅₀be 220 μm, d ₉₀be 300 μm, temperature of fusion Tm is 160 DEG C, F ₃₀melt strength is 6.5cN and v ₃₀melt extensibility is the straight chain alfon of 160mm/s.

L-PP3 is MFR ₂(230 DEG C) are 3.39g/10min, d ₅₀be 700 μm, d ₉₀be 1,100 μm, temperature of fusion Tm is 159 DEG C, F ₃₀melt strength is 8.2cN and v ₃₀melt extensibility is the straight chain alfon of 155mm/s.

Additive agent mixture

Linear polypropylene 1-PP2 is used for providing additive agent mixture (AM), and additive agent mixture (AM) comprises as masterbatch further to be mixed into the additive of branched polypropylene matrix polymer.Additive agent mixture comprises the linear polypropylene l-PP1 of 87.50 % by weight, the Irganox B 225FF (antioxidant) of 10.00 % by weight and 2.50 % by weight hydrotalcites.

Example IE1 to IE5 of the present invention and comparative examples CE1:

The 1-PP1 of comparative examples CE1, the l-PP2 of example IE1 to IE4 of the present invention and the l-PP3 of example IE5 of the present invention are experienced reactive extrursion under the existence of divinyl and superoxide, as described below.By divinyl and superoxide (75% solution of the BPIC (t butyl peroxy isopropyl carbonate) " Trigonox BPIC-C75 " of Akzo Nobel) (amount illustrates in table 3) and l-PP1 powder or the pre-mixing at the temperature of 65 DEG C in the horizontal blender with paddle agitator of l-PP2 powder before melt blending processes, keep the mean residence time of 15 minutes to 20 minutes.Premixture to be transferred under an inert atmosphere a diameter be 60mm, L/D than be 48, the co-rotating twin screw extruder that high-density mixing screw is housed, there is the Theyson TSK60 type that 3 kneading disc and the exhaust of two steps are arranged.Melt temperature distribution provides in Table 1.Screw speed and throughput illustrate in table 2.Branched polypropylene (b-PP) is prepared at first 3/4 place of forcing machine length.Subsequently, by side feeder, namely at rear 1/4 place of forcing machine length, additive agent mixture is fed to forcing machine to prepare branched polypropylene (b-PP).The polypropene composition extruded is discharged and granulation.Film is prepared, as mentioned above (OCS gel index) by particle.Final character illustrates in table 3.

Table 1: the design temperature distribution in forcing machine

Region		1 to 6	7	8 and 9	10 and 11	12	13	14
									Temperature	[℃]	240	230	220	230	230	220	230

Table 2: processing condition

		IE 1	IE 2	IE 3	IE 4	IE 5	CE 1
								Superoxide *	[% by weight]	0.350	0.400	0.475	0.475	0.360	0.475
Divinyl *	[% by weight]	1.0	1.4	1.4	1.3	0.9	0.5
								Screw speed	[rpm]	400	400	400	400	450	400
Throughput	[kg/h]	225	225	225	225	225	225
								Additive agent mixture *	[% by weight]	2	2	2	2	2	2

* based on the total amount of polypropene composition

Table 3: the character of polypropene composition

	MFR 2	F 30	v 30	OCS gel index
						[g/10min]	[cN]	[mm/s]	[-]
IE1	8.7	7.0	256	29
					IE2	9.1	7.6	259	20
IE3	11.4	8.0	261	48
					IE4	10.2	8.3	269	117
IE5	8.9	8.1	239	83
					CE1	11.4	5.7	252	1785

Claims (19)

1. one kind provides the method for polypropene composition, described polypropene composition comprises at least 90 % by weight branched polypropylene (b-PP), described method at least comprises: step (a), polypropylene (PP) and thermolysis free radical forming agent and optional difunctionality unsaturated monomer and/or multifunctional unsaturated low-molecular weight polymer is wherein made to react, obtain described branched polypropylene (b-PP) thus

Wherein

The melt flow rate (MFR) MFR of (c) described polypropylene (PP) ₂(230 DEG C) are in 3.0 to 13.0g/10min scope;

D () described polypropene composition and/or described branched polypropylene (b-PP) have the F being greater than 5.8cN ₃₀melt strength and the v being greater than 200mm/s ₃₀melt extensibility, wherein said F ₃₀melt strength and described v ₃₀melt extensibility is measured according to ISO16790:2005.

2. method according to claim 1, wherein said polypropylene (PP)

A () is alfon;

And/or

B () preferably has the F being greater than 1.0cN for linear polypropylene (l-PP), described linear polypropylene (l-PP) ₃₀melt strength and the v lower than 200mm/s ₃₀melt extensibility, wherein said F ₃₀melt strength and described v ₃₀melt extensibility is measured according to ISO16790:2005.

3. method according to claim 2, wherein said linear polypropylene (l-PP) has being greater than the F in 1.0 to 65.0cN scope ₃₀melt strength and lower than 200mm/s, preferably lower than the v of 190mm/s ₃₀melt extensibility, wherein said F ₃₀melt strength and v ₃₀melt extensibility is measured according to ISO 16790:2005.

4. according to method in any one of the preceding claims wherein, wherein

A () described thermolysis free radical forming agent is superoxide;

And/or

B () described difunctionality unsaturated monomer is selected from the group be made up of divinyl compound, allylic cpd and dienes.

5. according to method in any one of the preceding claims wherein, wherein said method comprises another step (b) of then step (a), wherein in described branched polypropylene (b-PP), adds melt flow rate (MFR) MFR ₂(230 DEG C) polypropylene in 1 to 18g/10min scope (PP ').

6. method according to claim 5, wherein when described polypropylene (PP) and the reaction between described thermolysis free radical forming agent and optional described difunctionality unsaturated monomer have occurred at least 80%, start described step (b).

7. the method according to claim 5 or 6, wherein said polypropylene (PP ') is linear polypropylene (l-PP '), described linear polypropylene (l-PP ') preferably there is the F being greater than 1.0cN ₃₀melt strength and the v lower than 200mm/s ₃₀melt extensibility, more preferably has being greater than the F in 1.0 to 65.0cN scope ₃₀melt strength and the v lower than 200mm/s ₃₀melt extensibility, wherein said F ₃₀melt strength and described v ₃₀melt extensibility is measured according to ISO 16790:2005.

8. according to method in any one of the preceding claims wherein, and wherein said linear polypropylene (l-PP) and/or described linear polypropylene (l-PP ') have

(a) lower than 1, the size-grade distribution d of 500 μm ₉₀;

And/or

(b) lower than 1, the size-grade distribution d of 000 μm ₅₀;

And/or

(c) lower than 1.80 d ₉₀/ d ₅₀ratio.

9. according to method in any one of the preceding claims wherein, wherein said step (a) and optional described step (b) complete in an extruder, described forcing machine is preferably included in the first mixing region (MZ1) on direction of operating and the second mixing region (MZ2), wherein described step (a) occurs described first mixing region (MZ2) further, and described step (b) occurs described second mixing region (MZ2).

10. method according to claim 9, wherein said forcing machine is included in the opening for feed (FT) on direction of operating, described first mixing region (MZ1), described second mixing region (MZ2) and mould (D), wherein side opening for feed (SFT) is positioned between described first mixing region (MZ1) and described second mixing region (MZ2), wherein described polypropylene (PP) further, described thermolysis free radical forming agent and optional described difunctionality unsaturated monomer by (FT) charging of described opening for feed and described polypropylene (PP ') by opening for feed (SFT) charging of described side.

11. methods according to claim 9 or 10, wherein

A () described polypropylene (PP) and the reaction between described thermolysis free radical forming agent and optional described difunctionality unsaturated monomer occur in described first mixing region (MZ1);

And/or

Described branched polypropylene (b-PP) total amount of (b) described polypropene composition be not more than 10 % by weight in described second mixing region (MZ2) preparation.

12. methods according to any one of aforementioned claim 5 to 11, wherein polypropylene described in 1 to 5 weight part (PP ') is added branched polypropylene (b-PP) described in 95 to 99 weight parts, preferably wherein polypropylene described in 1 to 3 weight part (PP ') is added 97 to 99 weight part branched polypropylene (b-PP), more preferably wherein polypropylene described in 2 weight parts (PP ') is added branched polypropylene (b-PP) described in 98 weight parts.

13. according to method in any one of the preceding claims wherein, wherein

(a) described polypropylene (PP ') comprise at least one additive (A), described at least one additive (A) is selected from by the following group formed: antioxidant, metal passivator, UV stablizer, static inhibitor, antifogging agent, acid scavenger, whipping agent, caking agent, lubricant, nucleator, surface slip agent, release agent and its mixture;

And/or

B () described branched polypropylene (b-PP) is not containing additive (A).

14. methods according to any one of foregoing Claims, the described polypropene composition wherein generated has

(a) F in 5.8 to 20.0cN scope ₃₀melt strength and the v in 210 to 300mm/s scope ₃₀melt extensibility;

And/or

B () is less than 1, and 500, be preferably less than 1, the gel index of 000.

15. according to method in any one of the preceding claims wherein, and the described polypropene composition wherein generated limits further any one of claim 16 to 18.

16. 1 kinds of polypropene compositions, comprise

(b) 95 to 99 weight part branched polypropylene (b-PP); With

(b) 1 to 5 melt flow rate (MFR) MFR of measuring according to ISO 1133 of weight part ₂(230 DEG C) being greater than the polypropylene in 1.0 to 18.0g/10min scope (PP '),

Wherein said polypropene composition has

-in 7.0 to 13.0g/10min scope according to ISO 1133 measure melt flow rate (MFR) MFR ₂(230 DEG C); With

-lower than 1,000, preferably lower than 800 gel index;

With wherein said polypropene composition and/or described branched polypropylene (b-PP), there is the F in 5.8 to 13.0cN scope ₃₀melt strength and the v in 210 to 300mm/s scope ₃₀melt extensibility, wherein said F ₃₀melt strength and described v ₃₀melt extensibility is measured according to ISO 16790:2005.

17. polypropene compositions according to claim 16, wherein said polypropene composition comprises at least one additive (A), and described at least one additive (A) is selected from by the following group formed: antioxidant, metal passivator, UV stablizer, static inhibitor, antifogging agent, acid scavenger, whipping agent, caking agent, lubricant, nucleator, surface slip agent, release agent and its mixture.

18. methods according to any one of aforementioned claim 1 to 15 or the polypropene composition according to claim 16 or 17, wherein said polypropene composition and/or described branched polypropylene (b-PP) are at 3.0s ^-1strain rate and 2.5 the lower strain hardening coefficient (SHF) measured of prosperous base strain be at least 1.9, preferably in 1.9 to 7.0 scopes, more preferably in 1.9 to 6.5 scopes.

19. a film, described film comprises the polypropene composition according to any one of aforementioned claim 16 to 18.